The present invention is generally directed to imaging processes with toner and developer compositions, and more specifically the present invention is directed to imaging and printing processes with toner compositions, including magnetic, single component, and two component, developer compositions particularly useful for generating documents, such as personal checks, which are subsequently processed in reader/sorters, and wherein there is avoided or minimized the tampering of the characters present thereon. Documents, including legal documents, such as personal checks, birth certificates, automobile licenses, identification papers, and the like have been tampered with, modified, altered, forged, and the like by, for example, attempting to delete, or modify characters present on these documents. For example, with personal checks the individuals name, address, and the character numbers appearing thereon can be unlawfully altered and utilized without detection. These and other disadvantages are avoided or minimized with the processes of the present invention. In one embodiment of the present invention, there are provided processes that enable one to easily detect the tampering, changing, modification, including forgery, and the like of documents, such as checks, including for example dividend checks, turn around documents, such as invoice statements like those submitted to customers by American Express and VISA, corporate checks, highway tickets, rebate checks, other documents with magnetic images and codes thereon obtained with a magnetic toner as illustrated herein, which toner has included therein a dye. The aforementioned dye causes a noticeable permanent color change on the document when, for example, altering is attempted with a solvent. More specifically, in one embodiment the process of the present invention is accomplished with toner and developer compositions comprised of a resin, magnetite, a black or highly colored dye, and optional components such as low molecular weight hydrocarbons containing functional groups such as hydroxy, amides, amines, esters, or polymeric alcohols as illustrated herein, and wherein image smearing and offsetting of the toner is avoided to read and write heads, including offsetting to the protective foil that may be present on the aforesaid heads in magnetic ink character recognition processes and apparatus inclusive of, for example, the read and write heads present in MICR (magnetic ink character recognition) reader/sorters such as the commercially available IBM 3890.TM., NCR 6780.TM., reader/sorters from Burroughs Corporation, and the like; and wherein modification, or alteration and the like is avoided, or minimized when solvents such as acetone, toluene, chloroform, and the like are selected. Accordingly, with the processes utilizing the toner and developer compositions illustrated the problems of document tampering, forgery, alteration, and the like are eliminated or minimized since the dye present in the toner causes a noticeable highly visible color change on the document, or character image when treated with a solvent thereby preventing the documents from being presented or accepted by others, such as banks, and the like. Moreover, in another embodiment the present invention is directed to improved economical processes for generating substantially tamper proof documents such as personal checks obtained, for example, by magnetic image character recognition methods, and wherein a magnetic toner with a dye is selected for generating the aforementioned documents. The toner compositions selected for the process of the present invention in an embodiment are comprised of resin particles, pigment particles, including magnetic components such as magnetites, dyes such as organic soluble dyes, including for example nigrosine, methylene blue, Sudan Blue, Rhodamine dye, and the like, and as optional components certain waxes such as those containing hydroxyl functionality. In addition, the present invention is directed to processes with developer compositions comprised of the aforementioned toners, and carrier particles. Further, the processes of the present invention with the toner and developer compositions illustrated, including single component toners, enable reliable output copy quality and stable triboelectric charging properties for the toner compositions selected.
Image and character tampering of documents as illustrated is avoided or minimized with the processes of the present invention since when the fused image or characters are brought into contact with solvents such as toluene there is immediately generated a colored stain, such as a bright violet stain with a Rhodamine dye. Also, with the processes of the present invention offset is eliminated or minimized, it is believed, because of the presence of the additives, reference U.S. Pat. No. 4,859,550, the disclosure of which is totally incorporated herein by reference. Offset results from, for example, the developed toner image being removed from the MICR (magnetic ink character recognition) document, such as a check to the read and/or write heads contained in MICR readers such as the IBM 3890.TM. and the NCR 6780.TM.. When the aforesaid offset is eliminated or substantially reduced, the problem of image smearing onto the MICR documents, such as personal checks, is also avoided. Apparently, although it is not desired to be limited by theory the additive, such as the polymeric alcohol, functions as a lubricant against offset according to the aforementioned '550 patent. By offset is meant, for example, that the toner is released from the document, such as personal checks and transfers and sticks to the aforementioned read and/or write heads. As a result, toner is removed from the checks or other documents as illustrated herein primarily in a continuous manner causing image smearing, and substantially preventing the characters on the checks from being read magnetically and thus rejected in most instances. With the processes of the aforementioned patent, these problems are avoided, and more specifically the reject rate is less than one half of 1 percent for 5,000 checks processed through, for example, in the aforesaid IBM 3890.TM. reader/sorter 20 times (a reject amount of about 15 ). Thus, with the process of the above patent the reject rate is less than one half of 1 percent in embodiments thereof, it being noted that the acceptable reject rate usually does not exceed one half of 1 percent (0.5 percent), as determined by the American National Standards Institute (ANSI). Typically, the reject rate with the process of the above patent is from about 0.05 to about 0.3 percent depending, for example, on the sorter set up conditions as contrasted to a reject rate in excess of one half of 1 percent, which is not acceptable, with processes utilizing toner and developer compositions that contain, for example, no polymeric wax or other additives therein. With toner build up on the read/write heads, the excess toner is released to the check document being processed causing image smearing, which is avoided with the processes of the present invention.
With further respect to the present invention, the process is particularly applicable to avoiding or minimizing the unlawful modification of documents including personal checks, which have been fused with soft roll fusers. Fuser rolls, such as silicon rolls or other conformable fuser rolls, reference for example the soft fuser rolls incorporated into the Xerox Corporation 9700.TM. machine, are particularly useful with the processes of the present invention.
The documents, including the personal checks mentioned herein, can be obtained, for example, by generating a latent image thereon and subsequently developing the image, reference U.S. Pat. No. 4,517,268, the disclosure of which is totally incorporated herein by reference, with the toner and developer compositions illustrated herein, which toner also contains a dye therein that changes to a noticeable color on the document when treated with a solvent. The developed image that has been created, for example, in the Xerox Corporation 9700.TM. MICR printer, reference the aforesaid '268 patent, contains thereon, for example, the characters zero, 1, 2, 3, 4, 5, 6, 7, 8, and 9, and up to four symbols (E-13B and CMC-7 font), which characters are magnetically readable by the IBM 3890.TM., or other similar apparatus.
Developer and toner compositions with certain waxes therein are known. For example, there are disclosed in U.K. Patent Publication 1,442,835 toner compositions containing resin particles, and polyalkylene compounds, such as polyethylene and polypropylene of a molecular weight of from about 1,500 to 6,000, reference page 3, lines 97 to 119, which compositions prevent toner offsetting in electrostatic imaging processes. Additionally, the '835 publication discloses the addition of paraffin waxes together with or without a metal salt of a fatty acid, reference page 2, lines 55 to 58. In addition, many patents disclose the use of metal salts of fatty acids for incorporation into toner compositions, such as U.S. Pat. No. 3,655,374. Also, it is known that the aforementioned toner compositions with metal salts of fatty acids can be selected for electrostatic imaging methods wherein blade cleaning of the photoreceptor is accomplished, reference Palmeriti et al. U.S. Pat. No. 3,635,704, issued Jan. 18, 1972, the disclosure of which is totally incorporated herein by reference. Additionally, there are illustrated in U.S. Pat. No. 3,983,045 three component developer compositions comprising toner particles, a friction reducing material, and a finely divided nonsmearable abrasive material, reference column 4, beginning at line 31. Examples of friction reducing materials include saturated or unsaturated, substituted or unsubstituted, fatty acids preferably of from 8 to 35 carbon atoms, or metal salts of such fatty acids; fatty alcohols corresponding to said acids; mono and polyhydric alcohol esters of said acids and corresponding amides; polyethylene glycols and methoxy-polyethylene glycols; terephthalic acids; and the like, reference column 7, lines 13 to 43.
Described in U.S. Pat. No. 4,367,275 are methods of preventing offsetting of electrostatic images of the toner composition to the fuser roll, which toner subsequently offsets to supporting substrates such as papers wherein there are selected toner compositions containing specific external lubricants including various waxes, see column 5, lines 32 to 45, which waxes are substantially different in their properties and characteristics than the polymeric alcohol waxes selected for the toner and developer compositions of the present invention; and moreover, the toner compositions of the present invention with the aforementioned polymeric alcohol additives possess advantages, such as elimination of toner spotting, not, it is believed, achievable with the toner and developer compositions of the '275 patent.
Disclosed in copending application U.S. Pat. No. 004,939 now U.S. Pat. No. 4,883,736, the disclosure of which is totally incorporated herein by reference, are toner compositions including magnetic single component, and colored toner compositions containing certain polymeric alcohol waxes. More specifically, there is disclosed in the aforementioned patent the elimination of toner spots or comets with developer compositions comprised of toner compositions containing resin particles, particularly styrene butadiene resins, pigment particles such as magnetites, carbon blacks or mixtures thereof, polymeric hydroxy waxes available from Petrolite, which waxes can be incorporated into the toner compositions as internal additives or may be present as external components, it being noted that with the processes of the present invention these additives are usually present as internal components; and optional charge enhancing additives, particularly, for example, distearyl dimethyl ammonium methyl sulfate, reference U.S. Pat. No. 4,560,635, the disclosure of which is totally incorporated herein by reference, and carrier particles. As preferred carrier components for the aforementioned compositions, there are selected steel or ferrite materials, particularly with a polymeric coating thereover, including the coatings as illustrated in U.S. Pat. No. 751,922 (now abandoned), entitled Developer Composition with Specific Carrier Particles, the disclosure of which is totally incorporated herein by reference. One particularly preferred coating illustrated in the aforementioned copending application is comprised of a copolymer of vinyl chloride and trifluorochloroethylene with conductive substances dispersed in the polymeric coating inclusive of, for example, carbon black. One embodiment disclosed in the aforementioned abandoned application is a developer composition comprised of styrene butadiene copolymer resin particles, and charge enhancing additives selected from the group consisting of alkyl pyridinium halides, ammonium sulfates, and organic sulfate or sulfonate compositions; and carrier particles comprised of a core with a coating of vinyl copolymers, or vinyl homopolymers. The polymeric components of the aforesaid application are also selected for various embodiments of the present invention as illustrated herein.
In a Petrolite, Inc. brochure, dated 1985 there are disclosed polymeric hydroxy waxes, which brochure indicates that the waxes may have utility as toner.
In U.S. Pat. No. 4,517,268, and U.S. Pat. No. Re. 33,172, the disclosures of which are totally incorporated herein by reference, there is illustrated a process for generating documents such as personal checks suitable for magnetic image character recognition, which process involves generating documents in high speed electronic laser printing devices. The developer composition disclosed in this patent is comprised of, for example, magnetic particles, such as magnetite, certain styrene resin particles, and the carrier particles as illustrated in the Abstract of the Disclosure. Additive particles may also be included in the developer compositions of this patent. One object of the present invention is to provide toners and proceses whereby alteration, modification, tampering, including unlawful tampering, and the like are avoided or minimized with the toners and developers of the aforementioned patent that also contain a dye as illustrated herein.
Moreover, toner and developer compositions containing charge enhancing additives, especially additives which impart a positive charge to the toner resin, are well known. Thus, for example, there is described in U.S. Pat. No. 3,893,935 the use of certain quaternary ammonium salts as charge control agents for electrostatic toner compositions. There is also described in U.S. Pat. No. 2,986,521 reversal developer compositions comprised of toner resin particles coated with finely divided colloidal silica. According to the disclosure of this patent, the development of images on negatively charged surfaces is accomplished by applying a developer composition having a positively charged triboelectric relationship with respect to the colloidal silica. Further, there is illustrated in U.S. Pat. No. 4,338,390, the disclosure of which is totally incorporated herein by reference, developer and toner compositions having incorporated therein as charge enhancing additives organic sulfate and sulfonate compositions; and in U.S. Pat. No. 4,298,672, the disclosure of which is totally incorporated herein by reference, positively charged toner compositions containing resin particles and pigment particles, and as a charge enhancing additive alkyl pyridinium compounds, inclusive of cetyl pyridinium chloride.
Other prior art disclosing positively charged toner compositions with charge enhancing additives include U.S. Pat. No. 3,944,493; 4,007,293; 4,079,014 and 4,394,430.
Although the above described toner and developer compositions are useful for their intended purposes, there is a need for improved compositions. More specifically, there is a need for processes enabling the generation of documents, such as personal checks, with single and two component toner and developer compositions wherein character tampering, alteration, removal, forgery, and the like are eliminated in an embodiment of the present invention. There is also a need for the generation of developed images including the generation of personal checks in laser printers utilizing magnetic ink character recognition technology, wherein character tampering, alteration, removal, and the like are eliminated or minimized in an embodiment of the present invention, and wherein toner offset to protective foils present on the read and write heads is avoided, and image smearing is eliminated by adding to the toner, preferably as an internal additive, low molecular weight, less than about 20,000 weight average, aliphatic hydrocarbons; and especially polymeric alcohols. In addition, there is a need for MICR processes for generating documents such as personal checks with toner and developer compositions that maintain their triboelectrical characteristics for extended time periods exceeding, for example, 450,000 developed images, and wherein image tampering can be minimized.